JP2010513331A - Fluid sterilization and storage - Google Patents

Abstract

  The present invention adsorbs solid germicides, contaminants and releases active ingredients as a compounding agent applied separately, or sequentially, for sterilization and long-term storage of the fluid to be purified (6) It relates to a product comprising a composite substance (11). According to the invention, the active ingredient (13.1, 5.2) is used to adsorb contaminants (5.1, 5.2) from the fluid and / or at the same time sterilize and / or reduce contaminants (5.1, 5.2) in the fluid (6). By further processing the fluid (6) with the composite material (11) releasing 13.2), it becomes possible to maintain the activity of the solid fungicide. The products and methods according to the invention are particularly suitable for the sterilization and long-term storage of water / oil emulsions contaminated with sulfur-containing compounds.

Description

  The present invention relates to a product and process for sterilizing and long-term storage of a fluid to be purified.

  Similarly, fluids such as water, fuel, coolant, lubricant, and engine oil as well as physiological fluids are exposed to a wide variety of microorganisms due to environmental influences. In particular, fluids that are used for extended periods of time need to be protected from contamination by bacteria and fungi by adding bactericides and / or preservatives in order to maintain the desired fluid function.

  When liquid disinfectants or preservatives are used, microbial attack is prevented while adversely affecting the desired properties of the fluid. For example, when provided as bathing water or drinking water, only toxicologically acceptable disinfectants can be preserved or preserved because living organisms come into direct contact with fluids or even consume fluids. An additional element is that it can be used as an agent.

  However, when the disinfectant is used in solid form, the problems raised above are avoided. The disinfectant can be retained in the fluid tank in a convenient manner (eg, filtration, etc.) or may be incorporated directly into the filter system.

  U.S. Patent Application Publication No. 2003/0140785 describes a filter agent having an antibacterial action, comprising a particulate active polymer incorporated in a carrier. The active particles have a diameter of 0.1 to 5000 μm (micrometer). The active ingredient used is either metallic silver or silver combined with a complex. Since this silver is not released to the surroundings even if it is used, it has a catalytic effect. The polymer contains cross-linked polyacrylamide and an adsorbent fixed to them. The filter means is suitable for sterilizing fluids and is particularly suitable for sterilizing water or industrial liquids.

  US Pat. No. 5,792,793 describes an antimicrobial active ingredient that can be used on many carriers. The bactericidal effect of the active ingredient is attributed to the silver ions bound to the thiol complex. Suitable carriers are solid particles or liquids. In the present specification, the material used for the solid carrier is a wide variety of polymers and synthetic resins, specifically, synthetic acrylic resins. The particles have a diameter of 10 μm (micrometer) to 10 mm. Silver remains bound to the complex, and the complex is fixed to the carrier. The antibacterial active ingredient bound to the carrier can be used in a tank or for the treatment of water and can also be used in the medical field. The carrier particles herein can be freely introduced into the tank along with the fluid to be treated.

  However, it has been found that, depending on the composition of the fluid, the bactericidal properties of the surface active solid bactericidal agent are significantly reduced or even if the mechanism acts catalytically, the bactericidal properties are completely suppressed in a short time. Therefore, in order to maintain sterilization and storage efficacy, it becomes necessary to add additional sterilizing agents to the fluid. However, since a large amount of preservative is used excessively and its effectiveness is deactivated after a while, this treatment process affects the environment, and a great expense is generated.

  Thus, there remains a need for a process for sterilizing and long-term storage of fluids and corresponding sterilizing and preserving agents that do not have the disadvantages described above.

US Patent Application Publication No. 2003/0140785 US Pat. No. 5,792,793

  The object of the present invention is to provide a product related to the technical field described at the outset, which is toxicologically acceptable from an environmental point of view and further minimizes the consumption of fungicides and preservatives. It also provides a process that allows for sterilization and long-term storage of the fluid.

  The achievement of the object of the invention is realized by the features of claims 1 and 17. According to the present invention, in order to sterilize and preserve fluids, the product is used as a combination formulation based on a solid sterilant and a composite material that adsorbs contaminants and releases active ingredients. In this context, to improve the durability of the solid disinfectant, the fluid to be purified is further treated with a composite material that adsorbs the contaminants from the solution while simultaneously removing the contaminants in the fluid. Active ingredients are released for sterilization and / or reduction. Here, the combination formulation according to the present invention is used simultaneously, separately or alternately in the fluid to be purified.

  The product according to the invention and the treatment process have several advantages over the prior art. For example, removing contaminants from a fluid using a composite material ensures that the solid sterilant is not contaminated by the contaminants and its sterilization activity is not deactivated.

  Since the fungicides and / or preservatives used are solid, they can be easily filtered off. When sterilizing and preserving fluids used in fluid cycles (eg, cooling cycles, lubrication cycles, or drinking and bathing water treatment processes), the disinfectant and / or preservative may be, for example, one equal container or It is advantageous if it exists in only one tank. That is, on the one hand, it means that people who come into contact with the fluid do not come into contact with disinfectants, toxic substances for sterilization and storage, if necessary. On the other hand, the actual function of the fluid, i.e. the lubrication of the machine, ensures that it is not adversely affected by disinfectants or preservatives dissolved, emulsified or suspended in the fluid.

  Through the treatment process according to the present invention, the necessary amount of bactericides and / or preservatives can be minimized, so that the best low load on the environment is achieved.

  Preferably, the solid disinfectant used in the product consists of a single substance or a mixture of substances, and when these substances come into contact with microorganisms, in particular surface contact, the catalytic action provides a bactericidal effect on the microorganisms. It is. This ensures the sustained effect of the solid fungicide since it is not consumed in use. Specifically, the bactericidal and / or antibacterial effect can be obtained by bringing the solid bactericidal agent into contact with bacteria and / or fungi. This can be brought about, for example, by an oligodynamic effect based on the deleterious nature of metal cations on living cells. Specifically, for example, cations such as Hg, Ag, Cu, Sn, Fe, or Pb exhibit this effect. Especially in the case of engine oils, lubricants, cooling emulsions or in the medical field, it is important to completely prevent attacks by frequently occurring bacteria and fungi.

  The solid sterilant may also be used to sterilize in the sterilant by removing microorganisms from the fluid by adsorbing and releasing the active ingredient. This mechanism of action has the advantage that the fluid is protected against inert biological material.

  By adding the composite material into the fluid, at least some of the active ingredients present in the composite material are released into the fluid, and at the same time, contaminants in the fluid can enter the surface area of the composite material or within the composite material. Adsorbed. The two actions of this composite material result in effective removal of contaminants from the fluid. Thus, for example, contaminants that do not adsorb into the composite material due to the size or chemical structure of the contaminant are precipitated into the fluid by the released active ingredients or converted to an inactive form by a chemical reaction.

  At the same time, the release of the bactericidal active ingredient into the fluid sterilizes all microorganisms in a rapid sterilization process in fluids heavily contaminated with microorganisms. The newly emerging microorganisms in the fluid can then be removed without problems with a small amount of a suitable catalytic solid disinfectant.

  The product according to the invention and the treatment process according to the invention are particularly suitable for fluids containing contaminants that reduce the performance of surface active solid fungicides. The fluid itself may be, for example, in liquid or gaseous form and may consist of a single pure substance or a mixture of homogeneous or heterogeneous substances. A process for the purification of an emulsion, preferably comprising oil and water and used as a cooled lubricating emulsion, is particularly advantageous. Microorganisms such as bacteria present in such emulsions find the ideal conditions for growth and often produce multiple heterogeneous metabolites in the fluid, which metabolites, for example on the surface Locating them themselves can have a significant adverse effect on the bactericidal effect of the solid fungicide.

  Microorganisms that develop in oil-based emulsions produce, among other things, many sulfur-containing compounds, most of these sulfur-containing compounds emit malodors and have high affinity or reactivity with a number of substances such as metals. ing. Therefore, a composite material that adsorbs pollutants and releases active ingredients adsorbs and / or precipitates and / or precipitates sulfur and / or organic sulfur compounds and / or inorganic sulfur compounds present as pollutants in the fluid. It is advantageously configured to chemically convert to an inert form.

  Depending on the fluid to be purified, the composite material may be configured to adsorb and neutralize other contaminants, such as oxygen-containing or metal-containing compounds.

  If the active ingredient released from the complex substance causes the precipitation of pollutants in solid form and the released active ingredient further has an antibiotic effect, in particular a bactericidal and / or antibacterial effect, Further advantageous. Contaminant precipitation allows undesired substances to be separated by simple filtration, and as a result, the functioning of the fluid since the precipitated waste is no longer part of the fluid cycle, for example. Are maintained and the toxicological impact on the environment is reduced. In particular in the case of engine oils, lubricants, cooling emulsions, fluids in the sanitary or medical field, bacteria and fungal microorganisms can significantly change the properties of the fluid used, for example through acid release, or Since it can be a direct danger to humans in the medical field, it is essential to thoroughly control infections caused by this kind of microorganisms that occur frequently.

  The active ingredient released from the composite material is a particularly advantageous metal and / or metal compound, preferably Ag, in particular Cu and Zn. Metals and metal compounds have a particularly high affinity for many oxygen-containing compounds and sulfur-containing compounds. After release into the fluid to be purified, the pollutant therefore binds to the metal or metal compound and is neutralized or converted to an inert form by chemical reaction. Furthermore, many metals, especially Ag, as well as Cu or Zn, have a bactericidal effect, and when they are released into the fluid, the microorganisms present will be sterilized. Specifically, Ag ions are known to affect cell wall permeability and bind to sulfur bridges in proteins, resulting in impaired enzymatic function in the cell, Eventually, it can cause microbial death.

  Upon addition of the solid disinfectant to the fluid, it is preferred that no compounds, particularly metals or metal compounds, are released into the fluid. Specifically, it is understood that the amount of compound released in thermodynamic equilibrium per 9.8 g of solid fungicide is less than 2 μg / l. As a result, solid fungicides act only due to surface interactions with microorganisms. This catalytic mechanism of action indicates that no chemicals are consumed to develop a bactericidal effect. Thus, the solid disinfectant can remain in the fluid for a long time without reducing its activity, thereby reducing resource consumption and reducing the toxicological impact on the environment.

  With respect to composite materials that adsorb and release active ingredients, the object according to the invention is achieved in that the composite material contains a substrate and a metal or metal compound incorporated and / or bound thereto.

  Here, the metal includes, on the one hand, a metal atom and may exist as a cation, an anion, or nonionic type. On the other hand, however, the metals may be present as pure metal composites, eg composed of a plurality of metal atoms. The metal compound may be, for example, a metal complex or a metal-containing solid (eg, metal oxide, metal salt, or metal-containing zeolite). In the present specification, the metal-containing substance is an amorphous or crystalline particle, specifically, an amorphous or crystalline particle having a size in the nanometer region as an atomic or molecular form. It may be present in the form and / or in the form of a macroscopic solid, in particular in the form of a macroscopic solid having a size in the micrometer range.

  Preferably, Ag, and particularly preferably additional Zn and / or Cu, is present as a metal or a metal compound of a composite material that adsorbs and releases the active ingredient. This kind of metals and their compounds have a high affinity for many, especially oxygen-containing and sulfur-containing compounds, and the adsorption effect on this kind of pollutants is achieved by this composite material . Further, the existing metals have a sterilizing effect, and when added to the fluid, sterilize the existing microorganisms. The bactericidal effect is based on, inter alia, a micro-acting effect and causes a change in the osmotic pressure in the microorganism. Furthermore, especially Ag ions form hydroxy radicals through a catalytic mechanism, and in fluid they have a damaging effect on microorganisms as well.

  By using the base material, it is possible to intercalate dissimilar metals or other active substances in the base material without repeatedly developing the composite material. Metals or metal compounds are intercalated into the substrate, for example, by weak interactions (eg, van der Waals interactions or electrostatic interactions). In other aspects, the metals or metal compounds may be bonded to the substrate by chemical bonds (eg, covalent bonds or complex formation).

  Basically, suitable substrate materials are inorganic or organic compounds, which are converted into porous bodies of defined shape and size by suitable treatment and are chemically as possible. Inactive. In one advantageous embodiment, the substrate comprises a modified polysaccharide compound, particularly preferably further comprising polyacrylamide and / or an amine. This type of substrate is chemically inert in many fluids, especially water / oil emulsions.

  As a further aspect, a substrate having a precisely defined pore size and chemical composition may be used. For example, zeolite is suitable. As a result, it is possible to adsorb contaminants having a specific size or having specific chemical properties from the fluid in the intended manner. Chemical selectivity is thereby achieved, which prevents the composite material from unnecessarily absorbing contaminants and does not contaminate the solid fungicide at all. Therefore, it is possible to further reduce the consumption amount of chemical substances that are required.

  With regard to the solid fungicide, the object according to the invention is that the solid fungicide has an advantageous surface activity and is arranged and / or bonded to the substrate and on and / or near the surface of said substrate. This is achieved by containing a metal or a metal compound.

  As in the case of composite materials, the metals herein include, on the one hand, metal atoms and may exist as cation, anion or nonionic forms. On the other hand, however, the metals may exist as pure metal composites, eg composed of a plurality of metal atoms. The metal compound may be, for example, a metal complex or a metal-containing solid (eg, metal oxide, metal salt, or metal-containing zeolite). In the present specification, the metal-containing substance is an amorphous or crystalline particle, specifically, an amorphous or crystalline particle having a size in the nanometer region as an atomic or molecular form. It may be present in shape and / or in the form of a macroscopic solid, in particular a macroscopic solid having a size in the micrometer range.

  By accumulating in the area | region of the base-material surface, compared with the uniform distribution in all the base materials, the quantity of metals or metal compounds can be reduced significantly.

  It is also possible to attach the active ingredient near the surface rather than directly on the substrate surface. Furthermore, when a substrate having a porous structure is used, it can be controlled, for example, by the size of the pores, which are sufficient for the active ingredient due to their size. It is possible to pass through near pores. Therefore, for example, it is possible to use a surface active solid disinfectant capable of selectively disinfecting specific microorganisms.

  Basically, suitable base materials for solid fungicides are inorganic or organic compounds, which can be converted into a porous body of defined shape and size by appropriate processing. And as chemically inert as possible. In one advantageous embodiment, the substrate comprises alginic acid, preferably further comprising polyacrylamide and / or amine, and / or aluminum silicate or zeolite. Alginic acid or alginic acid salts are polymers of α-L-guluronic acid and β-D-mannuronic acid, which are very suitable for gel formation and are physiologically acceptable.

  In the solid fungicide, Ag is preferably present as a metal or in a metal compound, specifically, present as an Ag complex, and particularly preferably present as an Ag-amino complex. Ag and its compounds have a strong bactericidal effect against a very wide variety of microorganisms. Specifically, as described above in the composite material, Ag in an ionic form has a remarkable damage effect on living cells due to a small amount of effect.

  The solid fungicide and / or composite substrate is advantageously configured as a hydrogel, which is preferably swellable and / or elastic. Hydrogels are water-containing polymers but are themselves insoluble in water. Molecules and polymers in the hydrogel are joined, for example, by covalent or ionic bonds and / or by polymer chain looping to form a three-dimensional porous network. The hydrogel can physically swell without being dissolved in water by the hydrophilic polymer component. The fact that the hydrogel is highly biocompatible is particularly advantageous in the application of the inventive process in the medical field. At the same time, hydrogels also have high mechanical load carrying capacity and chemical stability, for example on strong flows and chemically aggressive fluids such as in lubricating emulsions, engine oils, cooling emulsions or corresponding fluid cycles. It means that it can be used without problems. High chemical stability is very advantageous, especially in solid fungicides, because the solid fungicide remains in the fluid to be cleaned over a long period of time and is attacked by various chemicals.

  Furthermore, the ability to swell has a positive effect on the adsorption properties of the composite material. The increase in volume as it swells creates openings and grooves in the hydrogel, resulting in rapid diffusion of contaminants from the fluid into the interior region of the composite. This demonstrates a high absorption capacity, meaning that contaminants are removed from the fluid in a short period of time. At the same time, swelling allows rapid release of the active substance into the fluid that is cleaned from the hydrogel. Both effects provide the best protection against solid fungicides by rapidly adsorbing contaminants and sterilizing the existing microorganisms in a short time by the released active substance.

  The solid fungicide and / or composite material is preferably present in the form of a polyhedron (eg, cube), flat plate, spherical particle, as a granule, as a granule, or as a coating on a carrier material, especially a container wall. The shape of the substance can be adjusted according to the intended application. In particular, a coating on the container wall is preferred. Thus, for example, a pure surface active solid disinfectant having a long-term effect may be applied as a coating on one wall of a fluid storage container, or a composite material that adsorbs and releases active ingredients may be added in the form of granules. Good. Therefore, the composite material can be removed again from the fluid after the effect is manifested.

  When the solid fungicide and / or the composite material are in the form of spherical particles or granular individual particles, they preferably have a diameter of 0.1 to 5 mm, specifically 0.5 to 1.2 mm. The surface of the material is consequently optimized depending on the volume. Thus, the surface active solid fungicide ensures that a surface that is large enough to come into contact with the microorganisms per mass of added material is obtained. In the case of the adsorbed composite material, it simultaneously ensures that there is a sufficient adsorption volume for the contaminants.

  The solid disinfectant and the composite material may in principle be added simultaneously to the fluid to be purified. This has the advantage that the fluid can be sterilized very easily and stored for a long time with a single addition of the product. However, in order to achieve the optimal effect of the product, in the first treatment process, the fluid to be purified is treated only with a complex substance that adsorbs and releases active ingredients, and only in the second treatment process the surface activity. It is advantageous to add a simple solid fungicide. Therefore, all contaminants and microorganisms are first removed from the fluid, and subsequently added solid germicide can exert its maximum effect. Later, if a large number of microorganisms or contaminants pass through the fluid already mixed with the solid disinfectant, to rapidly reduce the number of microorganisms and contaminants and hence maintain the disinfecting effect of the solid disinfectant In addition, it is of course possible to add again later the complex material which adsorbs and releases the active ingredient.

  Further advantageous embodiments and feature combinations of the invention result from the following detailed description and the entire claims.

  The drawings for explaining the embodiments are drawn schematically and schematically. In principle, the same parts are denoted by the same reference numerals.

It is a figure which shows the structure of a surface active solid disinfectant. It is a figure which shows the structure of the composite material which adsorb | sucks and discharge | releases an active component. It is the figure which added the solid disinfectant to the fluid contaminated with the pollutant. It is a figure which shows the fall of the sulfur concentration in aqueous solution and an emulsion with progress of time after adding a complex substance. It is a figure which shows the effect | action form of the composite substance which adsorb | sucks and discharge | releases an active component. It is a figure which shows the effect | action form of a solid germicide after removing the contaminant in a fluid.

  As shown in FIG. 1, the solid fungicide 1 consists of a substrate 2 made of organic components, sodium alginate, acrylamide, N, N′-methylenebisacrylamide, and, where appropriate, aluminum silicate. As the surface-active substance 3, an Ag-amino complex is introduced into a region near the surface of the substrate 2.

  FIG. 2 shows the structure of a composite material 11 that adsorbs and releases active ingredients. The substrate 12 is composed of a water-soluble modified polysaccharide, acrylamide, and N, N'-methylenebisacrylamide. The active ingredient 13.1 is incorporated therein in the form of an Ag-amino complex. As a further active ingredient 13.2, Zn is incorporated in metal form.

  FIG. 3 shows pollutants 5.1, 5.2 dissolved in a fluid 6 composed mainly of a wide variety of sulfur-containing compounds. These have a high affinity for the surface-active substance 3 and / or the Ag-amino complex of the solid fungicide 1. Therefore, the surface-active substance 3 is contaminated with the adsorbed contaminants 5.1.1 and 5.2.1 and loses the bactericidal action. However, in order to sterilize the fluid 6, it is indispensable that the bacterium 4.1 is in close contact with the surface active substance 3 of the solid sterilizer 1, as indicated by the bacterium 4.2. Bacteria 4.3 that come in contact with solid fungicides already occupied by adsorbed contaminants 5.1.1, 5.2.1 are not sterilized. The presence of very few uncontaminated surfactant 3 further increases the number of microorganisms through rapid growth, resulting in a large number of microorganisms 4.1 remaining in the fluid. .

Figure 4 shows S ² -concentration unit ppm (“parts per million”; vertical axis) in aqueous solution W (triangle plot) and emulsion E (square plot) as a function of time t (minute) (horizontal axis). Indicated. Here, the initial S ^2- concentration of both fluids at time t = 0 minutes is 1.4 ppm, and after t = 5 minutes, the concentration in emulsion E is less than 0.9 ppm and the concentration in aqueous solution W is 0.6 ppm. Decreased to less than At time t = 10 minutes, the S ²⁻ concentration was 0.4 ppm in Emulsion E and 0.3 ppm in aqueous solution W. t = 15 min after, about 0.2 ppm S ^2-were still present in both fluids. After t = 20 minutes, S ²⁻ was not detected in the aqueous solution W, but less than about 0.1 ppm of S ²⁻ was detected in the emulsion E. After 30 minutes, both solutions do not contain any S ²⁻ , ie the concentration is 0 ppm in each case.

  FIG. 5 shows the process in fluid in schematic form. When the composite material 11 is added into the fluid, the Ag-containing active ingredient 13.1 is partially released into the fluid 6. In the fluid 6, the active ingredients 13.1 react with the pollutants 5.1 and consequently they are converted to an inert form or settle and are located on the container wall 20 as solids. At the same time, the microorganism 4.1 is sterilized by the active ingredient 13.1. Furthermore, the composite material 11 is adsorbed with some contaminants 5.1 present in the fluid 6 by being combined with the active ingredient 13.1 still incorporated.

  FIG. 6 schematically shows the mechanism of action of the solid fungicide 1 on the microorganisms 4.1 dissolved in the fluid 6. The microorganisms 4.2 that come into contact with the solid fungicide 1 are sterilized by the catalyst and sterilization action of the surface active substance 3. They are then released again into the fluid 6 and are present in the form of inert biological material 4.4. By pre-treating the fluid 6 with the composite material 11, the contaminants are substantially absent and the surface 7 of the solid sterilant 1 is not contaminated, hence the long-term sterilizing effect of the fluid and / or Or it can be saved.

Solid fungicide (Example A): sodium alginate aqueous solution [12 ml, 4% (w / v), low viscosity, Sigma], water (5 ml), acrylamide aqueous solution (8 ml, 40% aqueous solution, purum, Fluka), Mix together N, N'-methylenebisacrylamide [4ml, 2% (w / v)] and N, N, N ', N'-tetramethylethylenediamine (0.1ml in 1ml water) Got. Spherical droplets having a diameter of 0.1 to 1.2 mm were formed from the solution using an encapsulation system (Nisco Engineering) having a die opening of 0.08 to 0.6 mm. While adding spherical droplets to ammonium peroxodisulfate solution (containing 80%, 1% (w / v), 0.1M calcium chloride) in a beaker stirred at 60 ° C, while spherical particles are formed Incubated for 30 minutes. The particles are separated from the curing solution by sieving, washed 5 times with 100 ml water, aged in aqueous sodium citrate (100 ml, 0.1 M) for 6 hours at room temperature (RT) and then 100 ml of Washed again 5 times with water. The citrate treatment and washing steps were repeated twice. The obtained spherical particles were boiled in an aqueous potassium hydroxide solution [500 ml, 5% (w / v)] for 5 hours. In parallel, prepare a 3-10% strength solution of Ag-amino complex containing AgNO ₃ and 2-methylaminopyridine and contain 50 ml of this solution containing spherical particles boiling at various temperatures Added to aqueous solution. After boiling for 4-12 hours and simultaneously removing ammonia, the spherical droplets are screened off, incubated 3 times for 2 hours each time with 5 liters of water, and finally dried at high temperature and vacuum. The mass of spherical particles of dried poly (acrylamide-co-potassium acrylate-co-N, N'-methylenebisacrylamide) is 7.8 ± 0.5mg, contacted with 10ml distilled water for 3 hours at room temperature Then it is 203 ± 10mg.

Solid disinfectant (Example B): sodium alginate aqueous solution [12 ml, 4% (w / v), low viscosity, Sigma], water (5 ml), acrylamide aqueous solution (8 ml, 40% aqueous solution, purum, Fluka), N, N'-methylene bisacrylamide [4ml, 2% (w / v ) ], and N, N, N ', N'- tetramethylethylenediamine (0.1 ml in 1 ml H ₂ O) were mixed together A solution was obtained. To this solution, 0.5 g of finely powdered aluminum silicate was added and stirred for 2.5 hours. From the solution, spherical droplets having a diameter of 0.1 to 1.2 mm were formed using an encapsulation system (manufactured by Nisco Engineering) having a mold opening of 0.08 to 0.6 mm. While adding spherical droplets to ammonium peroxydisulfate solution (containing 80%, 1% (w / v), 0.1M calcium chloride) in a beaker stirred at 60 ° C, while spherical particles are formed Incubated for 30 minutes. The particles are separated from the curing solution by sieving, washed 5 times with 100 ml water, aged in aqueous sodium citrate (100 ml, 0.1 M) for 6 hours at room temperature (RT) and then 100 ml of Washed again 5 times with water. The citrate treatment and washing steps were repeated twice. The resulting spherical particles were boiled in a 5% strength aqueous solution of AgNO ₃ , incubated for 45 minutes, washed 3 times for 2 hours each time with 5 liters of MilliQ water, and stored at 5 ° C. in water.

Composite material (Example C): An Ag-amino complex was synthesized by stoichiometrically mixing AgNO ₃ and aminopyridine. Subsequently, 80 ml of a 3% strength aqueous solution of the modified polysaccharide was mixed with 20 ml of an aqueous solution containing 1 to 15 g of an Ag-amino complex at 60 ° C. and heated for 30 minutes.

  From the solution, spherical droplets having a diameter of 0.1 to 1.2 mm were formed using an encapsulation system (manufactured by Nisco Engineering) having a mold opening of 0.08 to 0.6 mm. The spherical droplet was added to the fluid nitrogen in the beaker and stirred for 5 minutes. During this process, spherical particles were formed and separated from the fluid by sieving.

Complex material (Example D): water (5 ml), aqueous acrylamide solution (8 ml, 40% aqueous solution, purum, Fluka), N, N′-methylenebisacrylamide [4 ml, 2% (w / v)], and N , N, N ′, N′-tetramethylethylenediamine (0.1 ml in 1 ml of H ₂ O) was mixed to obtain a solution and heated at 50 ° C. for 30 minutes. Subsequently, 1.3 g of finely powdered Zn and 0.7 g of AgNO ₃ were added. From the solution, spherical droplets having a diameter of 0.1 to 1.2 mm were formed using an encapsulation system (manufactured by Nisco Engineering) having a mold opening of 0.08 to 0.6 mm. The spherical droplets are added to ammonium peroxydisulfate solution (containing 80%, 1% (w / v), 0.1 M calcium chloride) in a beaker stirred at 60 ° C. and incubated for 30 minutes, Spherical particles were formed.

  Comparative test (Example E): In the first test, various types of dirty, commercially available MOTOREX ™ cooled lubricating emulsions derived from water / oil are known from the prior art for comparison. Based on the treatment process present, the treatment was carried out with pure surface-active solid fungicide 1 and their biocidal ability was measured as a function of time. This calculated the number of bacteria per milliliter of the emulsion at different times after adding the solid fungicide. To improve the agitation, the emulsion was agitated or shaken in each case after addition of solid fungicide 1. To calculate the number of bacteria, in each case, three Petri dishes were coated with the same and defined aliquots and / or aliquots of emulsion and incubated for 24 hours. Subsequently, the number of bacteria on all three incubated aliquots was automatically calculated using an Acolyte® colony counter.

Table 1 shows a summary of the study. In the first test (No. 1), the number of bacteria 4.1 per ml of highly contaminated emulsion prior to treatment with solid fungicide 1 is greater than 10 × 10 ⁷ . After adding 39 mg solid fungicide per 50 ml emulsion and incubating for 72 hours, the number of bacteria dropped to 10 × 10 ² bacteria / ml. After 126 hours of incubation time, if no further solid fungicide 1 was added, the number of bacteria 4.1 increased again to 10 × 10 ⁴ bacteria / ml. In a second test (No. 2) using the same type of emulsion, the number of bacteria 4.1 after storage for 145 hours at room temperature before treatment with solid fungicide 1 is 10 × 10 ⁶ . After adding 156 mg solid fungicide per 45 ml emulsion and incubating for 48 hours, the number of bacteria dropped to 10 × 10 ⁴ per ml emulsion. However, the number of bacteria per ml after 196 hours of incubation was again 10 × 10 ⁶ and no longer changed after 300 hours of incubation.

  Two tests clearly showed that the emulsion used was sterilized for a long time with pure surface active solid fungicide 1 and could not be maintained. It is thought to be caused by contamination of the solid fungicide 1 due to the contaminants 5.1.1 and 5.2.1 derived from the emulsion. From the yellowish and / or brown discoloration of solid fungicide 1 in these tests, it is inferred that pollutants 5.1.1, 5.2.1 are at least partly sulfur-containing compounds. Sulfur-containing compounds are especially problematic due to the presence of bacteria or fungal 4.1 metabolites in the emulsion and these compounds have a high affinity for the Ag-containing solid fungicide 1 used.

  Desulfurization (Example F): Complex materials 11 that adsorb and release active components were examined in detail in a first test for their sulfur reducing power. In order to measure the sulfur reduction of the sulfur-containing fluid, the following test was conducted.

500 ml of water (distilled twice) was mixed with 1.4 ppm of sulfur (S ²⁻ ), each treated with 1 g of the composite material 11 (Example C) molded into a plate. During "desulfurization", it was used here raw aqueous solution having a concentration of S ^2-14 ppm from sodium sulphide.

  In each case, after 0, 5, 10, 15, 20, 25, and 30 minutes, the sulfur concentration was measured using spectroscopic methods with specific color detection means. The same test was performed using 500 ml of emulsion (Motorex® 7788) instead of water.

Subsequently, the composite material 11 that adsorbs and releases the active ingredient was used to sterilize various types of dirty, commercially available MOTOREX ™ cooled lubricating emulsions derived from water / oil. Prior to treatment, all emulsions 6 used have a high bacterial concentration of at least 10 × 10 ⁶ bacteria / ml. The same type of emulsion is contaminated here to varying degrees because it undergoes different processes. For sterilization and removal of contaminants 5.1, 5.2, in each case 100 mg of complex substance (Example D) per ml of emulsion was added to Emulsion 6 and at various times during the treatment process described above, Number was measured. Table 2 shows a summary of the tests performed and the results. It is clearly shown in the majority of emulsion 6 that bacteria 4.1 is no longer detected after 24 hours of incubation. After 6 days (6d), only one emulsion (7711) 6 still contains a small amount of bacteria 4.1, and after 20 days (20d), all of emulsion 6 does not contain bacteria 4.1. These results clearly show the bactericidal effect of the composite material.

Storage with solid fungicide (Example H): The storage effect of solid fungicide 1 was evaluated in the following test. Inoculate 1 liter of sterile Motorex ™ emulsion (type 7788) free of contaminants with 100 μl of emulsion containing bacteria of the same type (7788) to 10 × 10 ³ bacteria per ml, Mixed with spherical particles (mass = 7.8 mg) of solid fungicide (Example A). The number of bacteria 4.1 was measured at various times according to the above process. Table 3 shows the results of the test. From these results, it was clearly shown that solid fungicide 1 can completely reduce the bacterial concentration of 10 × 10 ³ bacteria / ml within 7 days and store the emulsion for 19 days. After 19 days, the sterilized emulsion was inoculated for the second time, but this time using 500μl of bacteria-containing emulsion (type 7788) to achieve a bacterial concentration of 50 × 10 ³ bacteria / ml. did. Two days after the second inoculation (t = 21 days), bacteria 4.1 grows significantly and is present at a concentration of 10 × 10 ⁶ bacteria / ml but decreases to 10 × 10 ² bacteria / ml after another 10 days. did. Tests clearly showed that emulsions sterilized and cleaned with complex materials can be stored for long periods with small amounts of solid fungicide. In this connection, the solid fungicide 1 can once again reduce the concentration increased to a maximum of 50 × 10 ³ bacteria / ml. However, when the bacterial concentration is high, the surface activity of the solid fungicide 1 is deactivated as described above.

  In a further advantageous refinement, Cu (II) complexes may be further added instead of Zn or together with Zn when preparing the composite material. This type of complex has a similar high affinity for sulfur-containing and oxygen-containing compounds and is added to complex 11 to optimize the adsorption effect for specific pollutants 5.1, 5.2, for example. May be. Ionic or neutral forms, or other metals bound to the compound, such as Hg, Sn, Fe or Pb may be mixed as bactericidal active ingredients and / or adsorbents.

  For use in fluid 6 under chemically extreme conditions and / or mechanically harsh conditions, for example, under high pressure, instead of or together with organic components (acrylamide, alginate, amine or polysaccharide) It is also possible to use another base material that forms or has a porous structure as the base material of the solid germicide 1 or the composite material 11. Certain inorganic compounds such as zeolite are preferred.

  As an alternative to encapsulation, solid disinfectants (Examples A and B) as well as composite materials (Examples C and D) are also suitable for use in, for example, fluid tanks or containers, plates, cubes, polyhedra, Or you may shape | mold into another shape. Specifically, together with the fluid 6 to be purified, a solid disinfectant having a lasting effect may be applied as a coating on the wall of the container.

  Solid disinfectant 1 or composite material 11 in the form of particles or granules may be incorporated into permeable materials, enclosures or cage structures in inert materials and fluids 6 so that individual particles or granules are contained in the fluid. And don't swim around freely.

As an alternative to the method described, the solid fungicide 1 may be added to the fluid 6 to be purified simultaneously with the composite material 11 that adsorbs and releases the active ingredient. This is possible because the purification and sterilization action of the composite material 11 starts very quickly, and contamination of the solid fungicide 1 with contaminants is a slower process. In this way, as is apparent from FIG. 4, the sulfur compounds in the emulsion (type 7788) are completely removed by the composite material 11 in as little as 30 minutes. Similarly, many of the same complex 11 emulsions examined in detail were free of bacteria after only 24 hours (see Table 2). As is apparent from Table 3, the solid disinfectant 1, briefly, that for several days, also acceptable to bacteria concentrations up 50 × 10 ³ bacteria / ml without simultaneously deactivate the surfactant and bactericidal action .

Instead of the described emulsion, it is also possible to treat other fluids 6 using the process according to the invention. Specifically, it has been found that an aqueous solution mixed with Escherichia coli (abbreviated as E. coli) can be sterilized and stored. E. coli, which can grow in physiological aqueous solutions, is a series of serious infections outside the human intestinal region, such as urinary tract infections, peritonitis (after peritoneal surgery), or meningitis in neonates (infection at birth) Disease). Specifically, E. coli bacteria were cultured in a Petri dish and diluted to a concentration of 10 ⁶ cells per milliliter using filtered Evian® water. Subsequently, solid fungicide 1 was added to this type of solution to a concentration of 99 mg / l. After 72 hours incubation time, the bacterial concentration was determined by the process indicated above. At this stage, E. coli was no longer detected. These results suggest that the process according to the present invention is also suitable for application in the medical field or in the hygiene field for the purpose of purifying drinking water or bathing water.

  In summary, new processes and formulations have been developed to sterilize and preserve fluids for long periods. This treatment process is based on the combination of the composite material 11 that adsorbs and releases the active ingredient and the solid fungicide 1 that is effective by catalytic action. The efficacy of the composite material 11 prevents contamination of the surface active solid fungicide 1 and consequently promotes a long-term effect. The products and processes according to the invention make it possible in particular to minimize the amount of fungicides and preservatives required.

1 Solid fungicide
2,12 Base material
3 Surface active substances
4.1, 4.2, 4.3 Microorganisms, bacteria
4.4 Inactive biological material
5.1, 5.2 Pollutants
5.1.1, 5.2.1 Adsorbed contaminants
6 Fluid
7 Surface of solid fungicide 1
11 Complex substances
13.1, 13.2 Active ingredient
20 container wall

Claims (17)

  Solid disinfectant (1) that adsorbs pollutants and releases active ingredients as a combined formulation applied simultaneously, separately or alternately during disinfection and long-term storage of the fluid to be purified (6) And products containing complex substances (11).   The solid fungicide (1) is configured to provide a bactericidal effect on the microorganism (4.1) by a catalytic mechanism when in contact with the microorganism (4.1), specifically surface contact, characterized in that Item 1. The product according to item 1.   The composite substance (11) adsorbs the pollutant (5.1, 5.2) from the fluid (6) and / or releases the active ingredient (13.1, 13.2), the active ingredient (13.1, 13.2) 5. Product according to claim 1 or 2, characterized in that it is configured to reduce 5.1, 5.2) and / or sterilize fluid (6).   4. Product according to any one of claims 1 to 3, wherein the fluid to be purified (6) containing said product is in the form of an emulsion, preferably consisting essentially of oil and water, A product characterized by being a cooling lubrication emulsion.   A complex substance (11) that adsorbs pollutants and releases active ingredients adsorbs sulfur and / or organic sulfur compounds and / or inorganic sulfur compounds present as pollutants (5.1, 5.2) of fluid (6) and 5. A product according to any one of the preceding claims, characterized in that it is configured to / or precipitate and / or be chemically converted to an inert form.   The active ingredient (13.1, 13.2) released from the compound (11) has an antibiotic effect, specifically a bactericidal and / or antibacterial effect, and the released active ingredient (13.1, 13.2) 2. Precipitating the pollutant (5.1, 5.2) in the fluid as a solid and / or converting the pollutant (5.1, 5.2) to an inert form by a chemical reaction. The product according to any one of -5.   The active ingredient (13.1, 13.2) released from the composite material (11) is a metal and / or metal compound, preferably Ag, in particular additionally Cu and / or Zn. The product according to any one of 1 to 6.   When the solid fungicide (1) is added to the fluid (6), the solid fungicide (1) is selected so that compounds, especially metals or metal compounds, are not released into the fluid (6) The product according to any one of claims 1 to 7.   The composite material (11) comprises a substrate (12) and an incorporated and / or bonded metal or metal compound (13.1, 13.2). Product described in.   10. Product according to claim 9, characterized in that the substrate (12) of the composite material (11) comprises a modified polysaccharide compound, preferably further comprising an acrylic polymer and / or an amine.   The solid disinfectant (1) comprises a base material (2) and a metal or metal compound (3) arranged and / or bonded on and / or near the surface of the base material, The product according to any one of claims 1 to 10.   12. The substrate (2) of the solid fungicide (1) comprises alginic acid, preferably further comprising polyacrylamide and / or amine, and / or aluminum silicate or zeolite. Product.   Ag is preferably present as a metal of the solid fungicide (1) or in the metal compound (3), and the metal is present in the form of an Ag complex, specifically an Ag-amino complex. 13. Product according to claim 11 or 12, characterized in that it is.   The substrate (2) of the solid disinfectant (1) and / or the substrate (12) of the composite material (11) is configured as a hydrogel, preferably having swelling and / or elasticity. The product according to any one of claims 9 to 13.   Solid disinfectant (1) and / or composite material (11) is present in the form of polyhedrons, cubes, plates, spherical particles, in the form of granules or as a coating on a carrier material, preferably a container wall The product according to any one of claims 1 to 14.   16. Product according to claim 15, characterized in that the spherical or granular individual particles have a diameter of 0.1-5 mm, preferably 0.5-1.2 mm.   In the first treatment process, the fluid to be purified (6) is treated with a complex substance (11) that adsorbs and releases active ingredients, and in the second treatment process, it is treated with a surface active solid fungicide (1). A fluid purification process using the product according to any one of claims 1 to 16, wherein

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